Polysulfonylamine, LXIV [1] Wasser-Dimere und Wasser-Monomere als Bindeglieder in Komplexen von 18-Krone-6 mit ungeladenen aciden Molekülen: Synthese und Kristallstrukturen

The ternary complexes 18C6-4H20 -2 H N ( S 0 2Ph)2 (3) and 18C 6-2H 20 2 H N ( S 0 2C6H44 F ) 2 (4) were obtained by co-crystallization of 18-crown-6 (18C6) with the appropriate di(arenesulfonyl)amine from aqueous solutions and characterized by low-temperature X-ray diffraction. The crystal structures consist of monomeric formula units displaying crystallographic C, symmetry for 3 (monoclinic, space group C2/c) and approximate C, symmetry for 4 (monoclinic, space group V2Jc). In 3, hydrogen-bonded water dimers H20 — H 0 'H (H O 182 pm) act as links between the two di(benzenesulfonyl)amine molecules and the crown ring. Each dimer accepts an N -H —O' bond (H --O' 194 pm) and is attached by its remaining protons to a set of three alternate crown oxygen atoms Oc (O 'H —Oc 202, OH O c 207 and 208 pm). The overall topological features of 3 strongly resemble those of the known supramolecule 18C6 • 2 MeOH • 2 H N (S 02Ph)2. In 4. each amine molecule is N H O bonded to a water monomer (H —O 184 and 187 pm) that is connected to two Oc atoms of the crown (O H O c 202-210 pm). The crown rings of both complexes adopt the frequently observed pseudo D 3d symmetry. In the crystal of the pure compound H N (S 0 2C6H4-4 -F )2 (5; monocli­ nic, space group C2/c), the molecules are associated into chains in the z direction through a relatively weak N H — O' bond (H -O ' 215 pm). The conformations of the H N (S 0 2R )2 entities in 3, 4, 5 and some related solids are compared and discussed.